LIPIDS

Introduction
• Lipids are a chemically diverse group of compounds, of which
the common and defining feature is their insolubility in water.
• The biological functions of the lipids are as diverse as their
chemistry.
• Fats and oils are the principal stored forms of energy in many
organisms.
• Phospholipids and sterols are major structural elements of
biological membranes.
• Other Lipids play crucial roles as enzyme cofactors, electron
carriers, light-absorbing pigments, hydrophobic anchors for
proteins, emulsifying agents in the digestive tract, hormones,
and intracellular messengers.
• We discuss Lipid here based on their Functional Roles
 Introduction to fatty acids
• Fatty acids are carboxylic acids with hydrocarbon
chains ranging from 4 to 36 carbons long (C4 to C36).
• In some fatty acids, this chain is unbranched and fully
saturated thus contains no double bonds.
• In others the chain contains one or more double bonds
thus unsaturated
• We can term fatty acids as long hydrocarbon chains of
various lengths and degrees of unsaturation with
carboxylic acid groups at the one end.
• The systematic name for a fatty acid is derived from the
name of its parent hydrocarbon by the substitution of
oic for the final e.
 Introduction to fatty acids
• For example, the C18 saturated fatty acid is called
octadecanoic acid because the parent hydrocarbon is
octadecane.
• A C18 fatty acid with one double bond is called
octadecenoic acid; with two double bonds,
octadecadienoic acid; and with three double bonds,
octadecatrienoic acid.
• Fatty acid carbon atoms are numbered starting at the
carboxyl terminus, as shown below.
• Carbon atoms 2 and 3 are often referred to as (alpha) α
and (beta) β, respectively.
• The methyl carbon atom at the distal end of the chain is
called the (omega) ω-carbon atom
Numbering fatty acid carbons
Fatty acid structure representation
 Introduction to fatty acids
• The position of a double bond is represented by the
Symbol delta (∆) followed by a superscript number.
• For example, cis- ∆9 means that there is a cis double bond
between carbon atoms 9 and 10.
• Trans- ∆2 means that there is a trans double bond between
carbon atoms 2 and 3.
• Alternatively, the position of a double bond can be denoted
by counting from the distal end, with the ω-carbon atom
(the methyl carbon) as number 1.
• Eicosapentaenoic acid (omega-3) shown in the previous
slide
 Introduction to fatty acids
• Fatty acids usually contain an even number of carbon
atoms, typically between 14 and 24.
• The 16- and 18-carbon fatty acids are most common.
• The hydrocarbon chain is almostly unbranched in
animal fatty acids.
• The alkyl chain may be saturated or it may contain one
or more double bonds.
• The configuration of the double bonds in most
unsaturated fatty acids is cis.
• The double bonds in polyunsaturated fatty acids are
separated by at least one methylene group.
 Introduction to fatty acids
• The double bonds of polyunsaturated fatty acids are almost
never conjugated (alternating single and double bonds, as
in –CH=CH-CH=CH-), but are separated by a methylene
group: -CH=CH-CH2-CH=CH-
• The properties of fatty acids and of lipids derived from
them are dependent on chain length and degree of
saturation.
• Unsaturated fatty acids those with double bond in the chain
have lower melting points than do saturated fatty acids of
the same length
 Introduction to fatty acids
• The melting point of stearic acid (18:0) is 69.68⁰C,
whereas that of oleic acid (18:1) is 13.48 ⁰C.
• The melting points of polyunsaturated fatty acids of the
C18 series are even lower.
• Chain length also affects the melting point, the melting
temperature of palmitic acid (C16) is 6.5 degrees lower
than that of stearic acid (C18).
• Thus, short chain length and unsaturation enhance the
fluidity of fatty acids and of their derivatives.
Some naturally occurring fatty acids in animals
 Storage Lipids
• The fats and oils are stored forms of fatty acids.
• One form of storage lipids constructed from fatty acids
are the triacylglycerols, also referred to as triglycerides,
fats, or neutral fats.
• Triacylglycerols are composed of three fatty acids each
in ester linkage with a single glycerol.
• Below are structures of glycerol and triacylglycerol
Glycerol
Triacylglycerol
 Storage lipids
• Triacylglycerols containing the same kind of fatty
acid in all three positions are called simple
triacylglycerols and are named after the fatty acid
they contain.
• Simple triacylglycerols of 16:0, 18:0, and 18:1, for
example, are tripalmitin, tristearin, and triolein.
• Most naturally occurring triacylglycerols are mixed;
they contain two or three different fatty acids.
• Triacylglycerols are stored for energy in cells called
adipocytes and they also for insulation.
• Triacylglycerols stored under the skin serve both as
energy stores and as insulation against low
temperatures.
 Storage lipids
• There are two significant advantages for storing
triacylglycerols as fuels, rather than polysaccharides.
• First, the carbon atoms of fatty acids are more reduced
than those of sugars, and oxidation of triacylglycerols
yields more than twice as much energy, gram for
gram, as the oxidation of carbohydrates.
• Second, because triacylglycerols are hydrophobic and
therefore unhydrated, the organism that carries fat as
fuel does not have to carry the extra weight of water
of hydration that is associated with stored
polysaccharides
 Storage lipids
• Most natural fats, such as those in vegetable oils, dairy
products, and animal fat, are complex mixtures of
simple and mixed triacylglycerols .
• They contain a variety of fatty acids differing in chain
length and degree of saturation.
• Vegetable oils are composed largely of triacylglycerols
with unsaturated fatty acids making them liquids at
room temperature.
• Triacylglycerols containing only saturated fatty acids,
such as tristearin, the major component of beef fat, are
greasy solids at room temperature.
 Storage lipids
• The other form of stored lipids are waxes.
• Waxes serve as stored energy and repellants
• Biological waxes are esters of long-chain (C14 to
C36) saturated and unsaturated fatty acids with long-
chain (C16 to C30) alcohols.
• Their melting points (60⁰ to 100⁰ C) are generally
higher than those of triacylglycerols.
• In plankton, waxes are the chief storage form of
metabolic fuel.
• Waxes have water repellant properties
• Certain skin glands of vertebrates secrete waxes to
protect hair and skin and keep it pliable, lubricated,
and waterproof.
 Storage lipids

• Example of biological wax is Triacontanoylpalmitate,

the major component of beeswax, is an ester of
palmitic acid with the alcohol triacontanol.
• Structure shown below
 Structural Lipids
• Structural lipids are found mostly in the biological
membranes.
• The central architectural feature of biological
membranes is a double layer of lipids.
• Membrane lipids are amphipathic: one end of the
molecule is hydrophobic, the other hydrophilic.
• The hydrophobic portions interact with each other and
the hydrophilic portions interact with water and direct
their packing into sheets called membrane bilayers.
• In following slides we consider some membrane lipids
 Structural lipids
• The three major kinds of membrane lipids are
phospholipids, glycolipids, and cholesterol.
• Phospholipids are abundant in all biological
membranes.
• A phospholipid molecule is constructed from four
components: one or more fatty acids, a platform to
which the fatty acids are attached, a phosphate, and an
alcohol attached to the phosphate as shown in Figure
below
 Structural lipids

• Schematic structure of a phospholipid.

 Structural lipids
• In the structure above the fatty acid components
provide a hydrophobic barrier, whereas the
remainder of the molecule has hydrophilic
properties that enable interaction with the aqueous
environment.
• The platform on which phospholipids are built may
be glycerol, a three-carbon alcohol, or sphingosine,
a more complex alcohol.
• Phospholipids derived from glycerol are called
phosphoglycerides.
• A phosphoglyceride consists of a glycerol backbone
to which are attached two fatty acid chains and a
phosphorylated alcohol.
 Structural lipids
• In phosphoglycerides, the hydroxyl groups at C-1 and
C-2 of glycerol are esterified to the carboxyl groups of
the two fatty acid chains.
• The C-3 hydroxyl group of the glycerol backbone is
esterified to phosphoric acid.
• When no further additions are made, the resulting
compound is phosphatidate (diacylglycerol 3-
phosphate), the simplest phosphoglyceride.
• Only small amounts of phosphatidate are present in
membranes.
• See below
 Structural lipids

• Phosphatide
 Structural lipids
• Phosphatide is a key intermediate in the biosynthesis of
the other phosphoglycerides.
• The major phosphoglycerides are derived from
phosphatidate by the formation of an ester bond between
the phosphate group of phosphatidate and the hydroxyl
group of one of several alcohols.
• The common alcohol moieties of phosphoglycerides are
amino acid serine, ethanolamine, choline, glycerol, and
inositol.
• The phosphoglycerids formed by these are:
• Phosphatidylserine, phosphatidylethanolamine,
phosphatidylcholine diphosphatidylglycerol and
phosphatidylinositol, respectively
 Structural lipids

• Sphingomyelin is a phospholipid found in membranes

that is not derived from glycerol.
• Instead, the backbone in sphingomyelin is sphingosine,
an amino alcohol that contains a long, unsaturated
hydrocarbon chain
 Structural lipids
• The second major class of membrane lipids, glycolipids,
are sugar-containing lipids.
• The simplest glycolipid, called a cerebroside, contains a
single sugar residue, either glucose or galactose.
• More-complex glycolipids, such as gangliosides,
contain a branched chain of as many as seven sugar
residues.
• Glycolipids are oriented in a asymmetric fashion with
the sugar residues always on the extracellular side of the
membrane.
 Structural lipids
• Cholesterol, the third major type of membrane lipid,
has a structure that is quite different from that of
phospholipids.
• It is a steroid, built from four linked hydrocarbon
rings.
 Structural lipids
• As mentioned earlier membranes are amphipathic
molecule containing hydrophobic and hydrophilic
moieties.
• Membrane formation is a consequence of the
amphipathic nature of the molecules.
• Their polar head groups favor contact with water,
whereas their hydrocarbon tails interact with one
another in preference to water.
• This leads to formation of a lipid bilayer shown
below
 Lipid bilayer

• The ball represent the polar head and green the non-
polar tail of the membrane structure.